Coloring agent comprising direct dyes and phosphate surfactants

ABSTRACT

Agents for coloring keratinic fibers, containing (a) at least one compound of formula (I) and (b) at least one phosphate surfactant are disclosed and described.

RELATED DOCUMENTS

The present application claims benefit The present application claimsbenefit and is a U.S. continuation patent application under 35 U.S.C.111(a) and claims the right of priority under 35 U.S.C. 365 tointernational patent Application No. PCT/EP2012/073247, filed Nov. 21,2012, entitled “Coloring Agent Comprising Direct Dyes and PhosphateSurfactants” which claims benefit of German application No.:102011089221.4, filed Dec. 20, 2011, these applications are hereinincorporated by reference in their entirety.

FIELD OF THE INVENTION

The present application generally relates to agents for coloring andoptionally lightening keratinic fibers, in particular human hair,containing specific cationic anthraquinone dyes and phosphatesurfactants. The application also generally relates to the use of theseagents to produce hair colors having increased shine, an intense colorresult, improved fastness properties, and reduced selectivity.

BACKGROUND OF THE INVENTION

Generally, either substantive dyes or oxidation dyes are used forcoloring keratinic fibers. Although intense colors with good fastnessproperties can be obtained with oxidation dyes, the development of thecolor generally takes place under the influence of oxidizing agents suchas H₂O₂ for example, which in some cases can damage the fiber.Furthermore, some oxidation dye precursors or certain mixtures ofoxidation dye precursors can have a sensitizing effect on people withsensitive skin. Substantive dyes are typically applied under gentlerconditions. The disadvantage of these dyes, however, is that the colorsoften have inadequate fastness properties, no only with regard to hairwashing, but also with respect to external influences like sunlight, orreactive environmental chemicals like swimming pool water. Such colorsare also generally significantly more sensitive to shampooing thanoxidative colors, so that an often undesired shift in shade or even avisible “decolorization” occurs much more quickly.

Achieving a uniform coloring of frequently pretreated hair, for examplebleached or permanently waved hair, where the fibers present differingdegrees of pre-damage, represents a particular challenge in terms ofcoloring hair with substantive dyes. During the coloring process itself,the coloring agent can exhibit an uneven coloring behavior ondifferently pre-damaged hair. Repeated hair washing can also cause thedyes to be washed out of the different areas of the hair to varyingdegrees, resulting in an inconsistent and undesirable color result.

In the development of coloring products based on substantive dyes thereis a particular focus on producing dye formulations having reducedselectivity, in order to achieve a uniform color result on sections ofthe hair that are damaged to varying degrees. In particular, thisreduced selectivity should still be present not only immediately afterthe coloring process but also after repeated hair washes.

BRIEF SUMMARY OF THE INVENTION

The present application provides a coloring agent (i.e. composition) forcoloring keratinic fibers, in particular human hair, which, in additionto other positive fastness properties, has a low selectivity (or a goodequalizing capacity) and good wash fastness.

The colors achieved with the agents according to the invention deliver abrilliant and intense color result, both immediately after the coloringprocess, and after repeated hair washes. Following application of thecoloring agent the hair can desirably be uniformly colored, even incases where the hair is damaged to varying degrees, wherein thisuniformity in the color result is still present even after repeated hairwashes. In particular, brilliant and neutral blue shades or shades inthe blue region with the advantageous fastness properties describedabove should be achieved, said shades also being outstandingly suitablefor matting. The agents additionally can desirably have an optimizedviscosity in terms of both the application process and the coloringcapacity.

DETAILED DESCRIPTION

The following detailed description of the invention is merely exemplaryin nature and is not intended to limit the invention or the applicationand uses of the invention. Furthermore, there is no intention to bebound by any theory presented in the preceding background of theinvention or the following detailed description of the invention.

The use of cationic anthraquinone dyes in products for coloringkeratinic fibers is already known in principle from the prior art, forexample from EP1006154 or EP1820826. Furthermore, combinations ofcationic anthraquinone dyes with oxidation dye precursors of thedeveloper type are claimed in EP 2 329 809 for the oxidative coloring ofhair.

Surprisingly it has been found that combinations of specific cationicanthraquinones as substantive dyes with phosphate surfactants lead tocolors which achieve the desired keratinic fiber coloring results to anoutstanding degree.

Combinations of the specific cationic anthraquinones according to thefirst subject matter disclosed herein with phosphate surfactants havenot yet been described in the prior art.

The present specification firstly provides an agent for coloring andoptionally lightening keratinic fibers, in particular human hair,wherein the agent contains in a cosmetic carrier

(a) a compound of formula (I)

-   -   wherein    -   the R1, the R2, and the R3 each independently of one another        denote a hydrogen, a halogen, a nitro group, a cyano group, a        carboxyl group, a sulfonic acid group, a hydroxyl group, a C₁-C₆        acyl amino group, a carboxamide group, a sulfonamide group, a        C₁-C₆ alkyl group, C₁-C₆ alkoxy group, a C₂-C₆ alkenyl group, a        C₂-C₆ hydroxyalkyl group, or a C₁-C₆ alkoxy C₂-C₆ alkyl group;    -   the R4, the R5, and the R6 each independently of one another        denote a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆        hydroxyalkyl group, or a C₁-C₆ alkoxy C₂-C₆ alkyl group;    -   the X, the Y, and the Z each independently of one another denote        a hydrogen or an N(R7)(R8) group,        -   wherein        -   the R7 and the R8 each independently of one another denote a            hydrogen, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a            C₂-C₆ hydroxyalkyl group, or a C₁-C₆ alkoxy C₂-C₆ alkyl            group,        -   and at least one of the X, the Y and the Z denote an            N(R7)(R8) group,    -   the n denotes a number from 2 to 6;    -   the A⁻ denotes a physiologically acceptable anion; and

(b) at least one phosphate surfactant.

The term “keratinic fibers” or “keratin fibers” may be usedinterchangeably and is understood to mean fur, wool, feathers and inparticular human hair. Although the agents according to the inventionare primarily suitable for dyeing keratin fibers, there is nothing inprinciple to preclude their use in other fields.

The term “coloring of keratin fibers” used according to the inventionincludes any form of color changing of fibers. It includes in particularthe color changes covered by the terms tinting, lightening, bleaching,peroxiding, oxidative coloring, semipermanent coloring, permanentcoloring and temporary coloring. It explicitly also includes colorchanges according to the invention presenting a lighter color result incomparison to the original color, such as for example coloring bleachingprocesses.

The agents (i.e. compositions) according to the invention contain theactive agents in a cosmetic carrier, preferably in a suitable aqueous,alcoholic or aqueous-alcoholic carrier. For the purposes of haircoloring such carriers include, for example, creams, emulsions, gels orsurfactant-containing foaming solutions, such as shampoos, foamaerosols, foam formulations or other preparations which are suitable foruse on the hair. It is also possible, however, for the agents accordingto the invention to be integrated into a formulation in powder or tabletform.

Within the meaning of the present specification aqueous-alcoholicsolutions are understood to be aqueous solutions containing 3 to 70 wt.% of a C₁ to C₄ alcohol, in particular ethanol or isopropanol. Theagents according to the invention can additionally contain furtherorganic solvents, such as for example methoxybutanol, benzyl alcohol,ethyl diglycol or 1,2-propylene glycol. All water-soluble organicsolvents are preferred here. An aqueous carrier contains within themeaning of the invention at least 30 wt. %, in particular at least 50wt. % of water, relative to the total weight of the agent. Aqueouscarriers are preferred according to the invention such that the agenthas a proportion of at least 80 wt. %, preferably at least 85 wt. %,relative to the total weight of the agent.

As the first ingredient (a) the agents according to the inventioncontain at least one substantive cationic anthraquinone dye of generalformula (I).

The substituents R1 to R8 of the compound of formula (I) are describedbelow by way of example: Examples of a C₁-C₆ alkyl group are the methyl,ethyl, propyl, isopropyl, n-butyl, s-butyl and t-butyl, n-pentyl andn-hexyl groups. Propyl, ethyl and methyl are preferred alkyl residues.Examples of a C₂-C₆ alkenyl group are vinyl, allyl, but-2-enyl,but-3-enyl and isobutenyl, preferred C₂-C₆ alkenyl residues being vinyland allyl. Preferred examples of a C₁-C₆ hydroxyalkyl group are ahydroxymethyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl,4-hydroxybutyl, 5-hydroxypentyl and 6-hydroxyhexyl group; a2-hydroxyethyl group is particularly preferred. C₁-C₆ alkoxy groups thatare preferred according to the invention are the methoxy or ethoxygroup. Examples of halogen atoms are F, Cl, Br or I atoms, with Br or Clatoms being most particularly preferred. Preferred examples of C₁-C₆alkoxy C₂-C₆ alkyl groups are the methoxyethyl, ethoxyethyl,methoxypropyl, methoxybutyl, ethoxypropyl, ethoxybutyl and methoxyhexylgroup. Examples of a C₁-C₆ acyl amino group are the acetamide group, thepropanamide group and the butanamide group, the acetamide group beingpreferred. The pyrrolidinium ring, the piperidinium ring, themorpholinium ring and the 1-azepanium ring can be mentioned as preferredexamples of a 5-, 6- or 7-membered ring formed from R4, R5 and thequaternary nitrogen atom.

Dyes of formula (I) in which R1, R2 and R3 independently of one anotherdenote a hydrogen, a halogen, a carboxyl group, a sulfonic acid group, aC₁-C₆ alkyl group, or a C₁-C₆ alkoxy group deliver particularly intensecolor results and are therefore preferred.

It is furthermore preferable for one of the residues selected from R1,R2 and R3 to denote a halogen, a carboxyl group, a sulfonic acid group,a C₁-C₆ alkyl group or a C₁-C₆ alkoxy group and for the other tworesidues selected from R1, R2 and R3 both to denote a hydrogen.

A preferred embodiment of the first subject matter of the invention isan agent for coloring and optionally lightening keratinic fibers, whichis characterized in that it contains a compound of formula (I) in whichat least one of the residues R1, R2 and/or R3 denotes a C₁-C₆ alkylgroup.

In the case of particularly suitable compounds of formula (I), one ofthe residues selected from R1, R2 and R3 denotes a C₁-C₆ alkyl group andthe other two residues selected from R1, R2 and R3 denote hydrogen.

In an explicitly most particularly preferred embodiment R1 and R2 bothdenote a hydrogen atom and R3 denotes a methyl group.

Furthermore, particularly good coloring results can be obtained withagents containing at least one compound of formula (I) in which theresidues R4, R5 and R6 independently of one another denote a C₁-C₆ alkylgroup or an alkenyl group. In particular, each of the residues R4, R5and R6 preferably denotes a C₁-C₆ alkyl group.

It is most particularly preferable for R4 and R5 both to denote a methylgroup and for R6 to denote a methyl group, an ethyl group or an n-propylgroup.

It is moreover most particularly preferable for R4 and R5 both to denotea methyl group and for R6 to denote an n-propyl group.

In a likewise particularly preferred embodiment the residues R4, R5 andR6 each denote a methyl group.

For compounds of formula (I) there is the proviso that at least one ofthe residues X, Y and Z denotes an N(R7)(R8) group. Colors having goodapplicational properties were obtained in particular when compounds offormula (I) were used in which X denotes an N(R7)(R8) group and Y and Zeach denote hydrogen.

In one embodiment, R7 and R8 preferably independently of one anotherdenote hydrogen or a C₁-C₆ alkyl group. R7 and R8 particularlypreferably independently of one another denote hydrogen or a methylgroup. Compounds of formula (I) in which both R7 and R8 denote hydrogenhave proved to be particularly suitable and are therefore particularlypreferred.

In the context of the work leading to the present technology it hasproved most particularly advantageous for X to denote an NH₂ group.

A further preferred embodiment is therefore an agent for coloring andoptionally lightening keratinic fibers, which is characterized in thatit contains a compound of formula (I) in which at least X denotes an NH₂group.

In one embodiment, n preferably denotes the numbers 2 or 3 and mostparticularly preferably the number 3.

In another embodiment, A⁻ denotes a physiologically acceptable anion.Suitable physiologically acceptable anions include halide, hydrogensulfate, sulfate, benzenesulfonate, p-toluenesulfonate, acetate,citrate, lactate, tartrate, methyl sulfate (H₃COSO₃), methyl sulfonateor trifluoromethane sulfonate. A⁻ particularly preferably denotesbromide or methyl sulfate (H₃COSO₃), with A⁻ most particularlypreferably denoting methyl sulfate (H₃COSO₃ ⁻).

Agents for coloring and optionally simultaneously lightening keratinicfibers that are preferred according to the invention are characterizedin that they contain at least one compound of general formula (I)selected from

-   -   3-[(4-amino-9,10-dihydro-3-methyl-9,10-dioxo-1-anthracenyl)amino]-N,N,N-trimethyl-1-propanaminium        methyl sulfate    -   3-[(4-amino-9,10-dihydro-3-methyl-9,10-dioxo-1-anthracenyl)amino]-N,N,N-trimethyl-1-propanaminium        bromide,    -   3-[(4-amino-9,10-dihydro-3-methyl-9,10-dioxo-1-anthracenyl)amino]-N,N,N-trimethyl-1-propanaminium        chloride,    -   3-[(4-amino-9,10-dihydro-3-methyl-9,10-dioxo-1-anthracenyl)amino]-N,N,N-trimethyl-1-propanaminium-p-toluenesulfonate,    -   3-[(4-amino-9,10-dihydro-3-methyl-9,10-dioxo-1-anthracenyl)amino]-N,N,N-trimethyl-1-propanaminium        acetate,    -   3-{([9,10-dihydro-4-(methylamino)-9,10-dioxo-1-anthracenyl]amino}-N,N-dimethyl-N-propyl-1-propanaminium        methyl sulfate,    -   3-{([9,10-dihydro-4-(methylamino)-9,10-dioxo-1-anthracenyl]amino}-N,N-dimethyl-N-propyl-1-propanaminium        bromide,    -   3-{([9,10-dihydro-4-(methylamino)-9,10-dioxo-1-anthracenyl]amino}-N,N-dimethyl-N-propyl-1-propanaminium        chloride,    -   3-{([9,10-dihydro-4-(methylamino)-9,10-dioxo-1-anthracenyl]amino}-N,N-dimethyl-N-propyl-1-propanaminium-p-toluenesulfonate        and    -   3-{([9,10-dihydro-4-(methylamino)-9,10-dioxo-1-anthracenyl]amino}-N,N-dimethyl-N-propyl-1-propanaminium        acetate.

The compound of the formula (Ia) was ideally suitable for achieving thedesired results,

in which A⁻ denotes a physiologically acceptable anion, preferablymethyl sulfate (H₃COSO₃ ⁻). The compound (Ia) in which A⁻ denotes methylsulfate is also known under the name Cationic Blue 347.

A further particularly preferred embodiment is therefore an agent forcoloring and optionally lightening keratinic fibers, which ischaracterized in that it contains as the compound of formula (I) acompound according to formula (Ia),

in which A⁻ denotes a physiologically acceptable anion, preferablymethyl sulfate (H₃COSO₃ ⁻).

The agents according to the present technology for coloring andoptionally simultaneously lightening keratin fibers include thecompound(s) of formula (I) preferably in amounts above 0.0001 wt. % andbelow 5 wt. %, relative in each case to the total agent.

A further preferred embodiment is an agent which contains thecompound(s) of formula (I) in a proportion from 0.0001 to 5 wt. %,preferably 0.005 to 3.5 wt. %, particularly preferably 0.01 to 2.5 wt.%, in particular 0.05 to 1.5 wt. %, and in particular preferably from0.01 to 1.0 wt. %, relative in each case to the total weight of theagent.

As the second constituent of the formulation (b) the agents include atleast one phosphate surfactant.

As used herein, the term “phosphate surfactants” refers to compoundswhich include at least one hydrophobic molecule part of mostlylong-chain alkyl residues, and also have a hydrophilic part having aphosphate group and optionally polyethylene oxide and/or polypropyleneoxide units.

C₈-C₃₀ alkyl residues, particularly preferably C₁₂-C₂₄ alkyl residues,which can be saturated or unsaturated and optionally branched, arepreferably used as the hydrophobic part. Depending on the source andproduction, it is preferable to use a mixture of compounds havingdiffering alkyl chain lengths as the phosphate surfactant.

The phosphate surfactants can be used either in their protonated form(i.e. acid form), or in the form of corresponding phosphate salts, withalkali metal ions, ammonium ions, mono-/di- or tri-alkyl ammonium ionsand mono-/di- or tri-(hydroxyalkyl)ammonium ions being preferred assuitable counterions. Particularly preferred phosphate surfactants areused as the free acid or as the sodium salt, ammonium salt,ethanolammonium salt (MEA), diethanolammonium salt (DEA) ortriethanolammonium salt (TEA).

The hydrophilic part of the phosphate surfactant can optionally comprisepolyethylene oxide and/or polypropylene oxide units in addition to thephosphate group. Phosphate surfactants are preferred which have 1 to 15,but preferably 3 to 10 ethylene oxide units, and/or have 1 to 10, butpreferably 3 to 8 propylene oxide units.

A further embodiment of the first subject matter of the presenttechnology is an agent wherein the phosphate surfactant comprises atleast one compound selected from C₈-C₃₀ alkyl phosphate, C₈-C₃₀ alkylether phosphate, di(C₈-C₃₀ alkyl)phosphate and/or mixtures thereof,preferably selected from C₁₂-C₂₄ alkyl phosphate, C₁₂-C₂₄ alkyl etherphosphate, di(C₁₂-C₂₄ alkyl)phosphate and/or mixtures thereof.

Examples of suitable C₈-C₃₀ alkyl phosphates include decyl phosphate,lauryl phosphate, C₁₂-C₁₃ alkyl phosphate, myristyl phosphate, cetylphosphate, stearyl phosphate, isostearyl phosphate, cetearyl phosphate,oleyl phosphate and behenyl phosphate.

Examples of suitable C₈-C₃₀ alkyl ether phosphates include Deceth-3phosphate, Deceth-4 phosphate, Deceth-5 phosphate, Deceth-8 phosphate,Deceth-10 phosphate, Deceth-12 phosphate, Deceth-15 phosphate, Laureth-3phosphate, Laureth-4 phosphate, Laureth-5 phosphate, Laureth-8phosphate, Laureth-10 phosphate, Laureth-12 phosphate, Laureth-15phosphate, Ceteth-3 phosphate, Ceteth-4 phosphate, Ceteth-5 phosphate,Ceteth-8 phosphate, Ceteth-10 phosphate, Ceteth-12 phosphate, Ceteth-15phosphate, Steareth-3 phosphate, Steareth-4 phosphate, Steareth-5phosphate, Steareth-8 phosphate, Steareth-10 phosphate, Steareth-12phosphate, Steareth-15 phosphate, Ceteareth-3 phosphate, Ceteareth-4phosphate, Ceteareth-5 phosphate, Ceteareth-8 phosphate, Ceteareth-10phosphate, Ceteareth-12 phosphate, Ceteareth-15 phosphate, Oleth-3phosphate, Oleth-4 phosphate, Oleth-5 phosphate, Oleth-8 phosphate,Oleth-10 phosphate, Oleth-12 phosphate, Oleth-15 phosphate,PPG-3-Ceteth-10 phosphate, PPG-3-Ceteth-15 phosphate, PPG-5-Ceteth-10phosphate, PPG-5-Ceteth-15 phosphate, PPG-3-Oleth-10 phosphate,PPG-3-Oleth-15 phosphate, PPG-5-Oleth-10 phosphate and PPG-5-Oleth-15phosphate.

Examples of suitable di(C₈-C₃₀) alkyl phosphates include didecylphosphate, dilauryl phosphate, di(C₁₂-C₁₃ alkyl)phosphate, dimyristylphosphate, dicetyl phosphate, distearyl phosphate, diisostearylphosphate, dicetearyl phosphate, dioleyl phosphate and dibehenylphosphate.

Particularly advantageous results with respect to color uptake andeffect on the fibers are achieved with mixtures of C₈-C₃₀ alkyl etherphosphate and di(C₈-C₃₀ alkyl)phosphate. Particularly advantageousphosphate surfactants are mixtures of C₈-C₃₀ alkyl ether phosphate anddi(C₈-C₃₀) alkyl phosphate.

Examples of particularly preferred phosphate surfactants are mixtures ofOleth-5 phosphate and dioleyl phosphate as well as of dicetyl phosphateand Ceteth-10 phosphate.

A further embodiment of the first subject matter of the presenttechnology is an agent wherein the phosphate surfactant comprises amixture of at least one C₈-C₃₀ alkyl ether phosphate and at least onedi(C₈-C₃₀ alkyl)phosphate, preferably a mixture of at least one C₁₂-C₂₄alkyl ether phosphate and at least one di(C₁₂-C₂₄ alkyl)phosphate.

The phosphate surfactants are preferably present in the agent in aproportion which ensures an optimum care performance on the hair, whichcorrespondingly supports the solubility or emulsifiability of furtheringredients and which adjusts the viscosity of the agents. At the sametime, the content of phosphate surfactants should be kept as low aspossible to save on raw materials and to guard against excessivedegreasing of the skin.

A further embodiment of the first subject matter of the presenttechnology is an agent wherein the phosphate surfactant comprises aproportion from 0.01 to 15 wt. %, preferably 0.05 to 12 wt. %,particularly preferably 0.1 to 10.0 wt. %, in particular 0.5 to 8.0 wt.%, and in particular preferably from 1.0 to 7.5 wt. %, relative in eachcase to the total weight of the agent.

In a further preferred embodiment, the agent further comprises at leastone further substantive dye. Substantive dyes can be divided intoanionic, cationic and non-ionic substantive dyes. The substantive dyesare preferably selected from nitrophenylenediamines, nitroaminophenols,azo dyes, anthraquinones, triarylmethane dyes or indophenols andphysiologically acceptable salts thereof. The additional substantivedyes are each preferably used in a proportion from 0.001 to 2 wt. %,relative to the total application preparation.

Preferred anionic substantive dyes include the compounds known under theinternational names or trade names Acid Yellow 1, Yellow 10, Acid Yellow23, Acid Yellow 36, Acid Orange 7, Acid Red 33, Acid Red 52, Pigment Red57:1, Acid Blue 7, Acid Green 50, Acid Violet 43, Acid Black 1, AcidBlack 52, bromophenol blue and tetrabromophenol blue.

Preferred cationic substantive dyes include cationic triphenylmethanedyes, such as for example Basic Blue 7, Basic Blue 26, Basic Violet 2and Basic Violet 14, aromatic systems which are substituted with aquaternary nitrogen group, such as for example Basic Yellow 57, BasicRed 76, Basic Blue 99, Basic Brown 16 and Basic Brown 17, as well assubstantive dyes containing a heterocyclic compound having at least onequaternary nitrogen atom, in particular Basic Yellow 87, Basic Orange 31and Basic Red 51. The cationic substantive dyes sold under the Arianortrademark are likewise preferred cationic substantive dyes according tothe invention.

Non-ionic nitro and quinone dyes and neutral azo dyes in particular aresuitable as non-ionic substantive dyes. Preferred non-ionic substantivedyes include the compounds known under the international names or tradenames HC Yellow 2, HC Yellow 4, HC Yellow 5, HC Yellow 6, HC Yellow 12,HC Orange 1, Disperse Orange 3, HC Red 1, HC Red 3, HC Red 7, HC Red 10,HC Red 11, HC Red 13, HC Red BN, HC Blue 2, HC Blue 11, HC Blue 12,Disperse Blue 3, HC Violet 1, Disperse Violet 1, Disperse Violet 4,Disperse Black 9, as well as 1,4-diamino-2-nitrobenzene,2-amino-4-nitrophenol, 1,4-bis-(2-hydroxyethyl)amino-2-nitrobenzene,3-nitro-4-(2-hydroxyethyl)aminophenol,2-(2-hydroxyethyl)amino-4,6-dinitrophenol,4-[(2-hydroxyethyl)amino]-3-nitro-1-methylbenzene,1-amino-4-(2-hydroxyethyl)amino-5-chloro-2-nitrobenzene,4-amino-3-nitrophenol, 1-(2′-ureidoethyl)amino-4-nitrobenzene,2-[(4-amino-2-nitrophenyl)amino]benzoic acid,4-[(3-hydroxypropyl)amino]-3-nitrophenol, 4-nitro-o-phenylenediamine,6-nitro-1,2,3,4-tetrahydroquinoxaline, 2-hydroxy-1,4-naphthoquinone,picramic acid and salts thereof, 2-amino-6-chloro-4-nitrophenol,4-ethylamino-3-nitrobenzoic acid and2-chloro-6-ethylamino-4-nitrophenol.

Coloring results with outstanding color intensity, brilliance and goodwash fastness can be particularly obtained in particular if the agentfurther comprises a substantive dye selected from D&C Red No. 33 (AcidRed 33), Acid Black No. 1, D&C Orange No. 4 (Acid Orange No. 4), AcidRed 18, Basic Red 76, Acid Violet 43, HC Blue No. 12,N-(2-hydroxethyl)-4-methyl-2-nitroaniline (Methyl Yellow), HC Yellow No.2, Red B 54 and 2-amino-6-chloro-4-phenol.

The agents can moreover also be used as oxidation coloring agents. Suchoxidation coloring agents additionally contain at least one oxidationdye precursor, preferably at least one oxidation dye precursor of thedeveloper type and at least one oxidation dye precursor of the couplertype. Particularly suitable oxidation dye precursors of the developertype are selected from at least one compound from the group formed fromp-phenylenediamine, p-toluylenediamine,2-(2-hydroxyethyl)-p-phenylenediamine,2-(1,2-dihydroxyethyl)-p-phenylenediamine,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,2-methoxymethyl-p-phenylenediamine,N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine,N,N′-bis-(2-hydroxyethyl)-N,N′-bis-(4-aminophenyl)-1,3-diaminopropan-2-ol,bis-(2-hydroxy-5-aminophenyl)methane,1,3-bis-(2,5-diaminophenoxy)propan-2-ol,N,N′-bis-(4-aminophenyl)-1,4-diazacycloheptane,1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane, p-aminophenol,4-amino-3-methylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(1,2-dihydroxyethyl)phenol,4-amino-2-(diethylaminomethyl)phenol,4,5-diamino-1-(2-hydroxyethyl)pyrazole, 2,4,5,6-tetraaminopyrimidine,4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,2,3-diamino-6,7-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-one and thephysiologically acceptable salts thereof.

Particularly suitable oxidation dye precursors of the coupler type areselected from the group comprising 3-aminophenol,5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol,2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol,5-(2-hydroxyethyl)amino-2-methylphenol, 2,4-dichloro-3-aminophenol,2-aminophenol, 3-phenylenediamine, 2-(2,4-diaminophenoxy)ethanol,1,3-bis(2,4-diaminophenoxy)propane,1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene,1,3-bis(2,4-diaminophenyl)propane,2,6-bis(2′-hydroxyethylamino)-1-methylbenzene,2-({3-[(2-hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol,2-({3-[(2-hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol,2-({3-[(2-hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol,2-[3-morpholin-4-ylphenyl)amino]ethanol,3-amino-4-(2-methoxyethoxy)-5-methylphenylamine,1-amino-3-bis-(2-hydroxyethyl)aminobenzene, resorcinol,2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene,2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine,1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,1,8-dihydroxynaphthalene, 4-hydroxyindole, 6-hydroxyindole,7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline, 7-hydroxyindolineor mixtures of these compounds or the physiologically acceptable saltsthereof.

The substantive dyes, developer components, and coupler components arepreferably each used in an amount from 0.0001 to 5.0 wt. %, preferably0.001 to 2.5 wt. %, relative in each case to the ready-to-use agent.Developer components and coupler components are generally used inapproximately molar amounts to one another. Although the molar use hasproved convenient, a certain excess of individual oxidation dyeprecursors is not disadvantageous, such that developer components andcoupler components can be in a molar ratio of 1 to 0.5 to 1 to 3, inparticular 1 to 1 to 1 to 2.

In the case of oxidation coloring agents the agents preferably containan oxidizing agent, preferably hydrogen peroxide. The amounts ofhydrogen peroxide correspond to the amounts in the lightening agentsaccording to the invention.

The agents can moreover be used as lightening coloring agents. In orderto achieve the lightening effect the agents contain hydrogen peroxideand/or one of the solid addition products thereof with organic orinorganic compounds.

A further embodiment of the first subject matter further compriseshydrogen peroxide and/or one of the solid addition products thereof withorganic or inorganic compounds.

In a preferred embodiment, hydrogen peroxide itself is preferably usedas an aqueous solution. The concentration of a hydrogen peroxidesolution in the agent is determined by legal requirements and by thedesired effect; 6 to 12 wt. % solutions in water are preferably used.Ready-to-use agents of a preferred embodiment comprise, relative to thetotal weight of the ready-to-use agent, 0.5 to 20 wt. %, preferably 1 to12.5 wt. %, particularly preferably 2.5 to 10 wt. % and in particular 3to 6 wt. % of hydrogen peroxide, relative in each case to the totalweight of the agent.

In order to achieve a stronger lightening and bleaching effect the agentcan moreover contain at least one peroxo salt. Suitable peroxo saltsinclude inorganic peroxo compounds, preferably selected from the groupformed from ammonium peroxodisulfate, alkali metal peroxodisulfates,ammonium peroxomonosulfate, alkali metal peroxomonosulfates, alkalimetal peroxodiphosphates and alkaline-earth metal peroxides.Peroxodisulfates are particularly preferred, in particular ammoniumperoxodisulfate, potassium peroxodisulfate, and sodium peroxodisulfate.

The persulfates are each included in the agent in an amount from 0.5 to20 wt. %, preferably 1 to 12.5 wt. %, particularly preferably 2.5 to 10wt. % and in particular 3 to 6 wt. %, relative to the total weight ofthe ready-to-use agent.

A further preferred embodiment is an agent for coloring and optionallylightening keratinic fibers, which further comprises hydrogen peroxide,one of the solid addition products thereof with organic or inorganiccompounds, ammonium peroxodisulfate, potassium peroxodisulfate and/orsodium peroxodisulfate, each in an amount from 0.5 to 20 wt. %,preferably 1 to 12.5 wt. %, particularly preferably 2.5 to 10 wt. % andin particular 3 to 6 wt. %, relative to the total weight of theready-to-use agent.

To strengthen the bleaching effect the agent can contain furtherbleaching strength intensifiers, such as for example tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine(DADHT), tetraacetyl glycoluril (TAGU), N-nonanoyl succinimide (NOSI),n-nonanoyl or isononanoyl oxybenzene sulfonate (n- or i-NOBS), phthalicacid anhydride, triacetin, ethylene glycol diacetate and2,5-diacetoxy-2,5-dihydrofuran as well as carbonate salts or hydrogencarbonate salts, in particular ammonium hydrogen carbonate, ammoniumcarbonate, sodium hydrogen carbonate, disodium carbonate, potassiumhydrogen carbonate, dipotassium carbonate and calcium carbonate, andnitrogen-containing, heterocyclic bleaching strength intensifiers, suchas 4-acetyl-1-methylpyridinium-p-toluenesulfonate,2-acetyl-1-methylpyridinium-p-toluenesulfonate as well asN-methyl-3,4-dihydroisoquinolinium-p-toluenesulfonate.

To further increase the lightening, at least one SiO₂ compound such assilicic acid or silicates, in particular water glasses, can additionallybe added to the composition according to the invention. It can bepreferable according to the invention to use the SiO₂ compounds inamounts from 0.05 wt. % to 15 wt. %, particularly preferably in amountsfrom 0.15 wt. % to 10 wt. % and most particularly preferably in amountsfrom 0.2 wt. % to 5 wt. %, relative in each case to the anhydrouscomposition . The specified amounts indicate the content of SiO₂compounds (excluding their water component) in the agents.

The ready-to-use coloring agents can moreover contain additional activeagents, auxiliary substances and additives to improve the coloringcapacity and to establish further desired properties of the agents.

The ready-to-use coloring agents are preferably provided as a liquidpreparation and therefore a further surface-active substance isadditionally added to the agents, the surface-active substances beingreferred to as surfactants or emulsifiers, depending on the field ofapplication. They are preferably selected from further anionic,cationic, non-ionic, amphoteric and zwitterionic surfactants andemulsifiers.

Agents that are preferred further comprise at least one further anionicsurfactant in addition to the phosphate surfactants. Preferred anionicsurfactants are fatty acids, alkyl sulfates, alkyl ether sulfates andether carboxylic acids with 10 to 20 C atoms in the alkyl group and upto 16 glycol ether groups in the molecule. The additional anionicsurfactants are used in proportions from 0.1 to 45 wt. %, preferably 1to 30 wt. % and most particularly preferably from 1 to 15 wt. %,relative to the total amount of the ready-to-use agent.

Agents that are preferred comprise at least one zwitterionic surfactant.Preferred zwitterionic surfactants are betaines,N-alkyl-N,N-dimethylammonium glycinates, N-acylaminopropyl-N,N-dimethylammonium glycinates, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines. A preferredzwitterionic surfactant is known under the INCI name CocamidopropylBetaine.

Addition products of ethylene oxide and/or propylene oxide with fattyalcohols, fatty acids, fatty acid amides, polyol esters of fatty acidsand polyol ethers of fatty alcohols as well as alkyl polyglucosides aresuitable in particular as non-ionic surfactants. Examples of suitablenon-ionic surfactants are Laureth-2, Beheneth-10, Ceteareth-12,Trideceth-12, Oleth-16, Ceteareth-20, Ceteareth-30 and Ceteareth-50 aswell as PPG-1 Trideceth-6, PEG-7 oleate, PEG-90 stearate, PEG-30cocoate, Polysorbate-20, Polysorbate-60, Polysorbate-65, Polysorbate-80,Polysorbate-85, lauryl glucoside, decyl glucoside and/or coco glucoside.

Agents that are preferred further comprise at least one amphotericsurfactant. Preferred amphoteric surfactants include N-alkyl glycines,N-alkyl propionic acids, N-alkyl aminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkyl amidopropyl glycines,N-alkyl taurines, N-alkyl sarcosines, 2-alkyl aminopropionic acids andalkyl aminoacetic acids. Particularly preferred amphoteric surfactantsinclude N-cocoalkyl aminopropionate, cocoacylaminoethyl aminopropionate,and C₁₂-C₁₈ acyl sarcosine.

The non-ionic, zwitterionic or amphoteric surfactants are used inproportions from 0.01 to 45 wt. %, preferably 0.1 to 30 wt. % and mostparticularly preferably from 1 to 15 wt. %, relative to the total amountof the ready-to-use agent.

Agents that are suitable for use can also contain cationic surfactantsof the quaternary ammonium compound, esterquat and amidoamine type.Preferred quaternary ammonium compounds are ammonium halides and theimidazolium compounds known under the INCI names Quaternium-27 andQuaternium-83. Further cationic surfactants which can be used accordingto the invention are the quaternized protein hydrolysates. A compoundfrom the amidoamines that is particularly suitable according to theinvention is the stearamidopropyl dimethylamine which is commerciallyavailable under the name Tegoamid® S 18. Preferred esterquats arequaternized ester salts of fatty acids with triethanolamine, quaternizedester salts of fatty acids with diethanol alkyl amines and quaternizedester salts of fatty acids with 1,2-dihydroxypropyl dialkylamines. Thecationic surfactants preferably comprise proportions from 0.05 to 10 wt.%, relative to the total agent.

The ready-to-use agents can contain further auxiliary substances andadditives. Thus it has proved advantageous if the agents contain atleast one thickening agent. There are no restrictions in principleregarding these thickening agents. Both organic and also purelyinorganic thickening agents can be used.

Suitable thickening agents include

-   -   cationic, synthetic polymers;    -   anionic, synthetic polymers, such as polyacrylates, acrylates        copolymer, copolymers of acrylic acid and methacrylic acid;    -   naturally occurring thickening agents, such as non-ionic guar        gums, scleroglucan gums or gum arabic, ghatti gum, karaya gum,        tragacanth gum, carrageen gum, carob seed meal, pectins, xanthan        gums, alginates, starch fractions and derivatives such as        amylose, amylopectin and dextrins, as well as cellulose        derivatives, such as for example carboxymethyl cellulose, methyl        cellulose and hydroxyalkyl celluloses;    -   non-ionic, fully synthetic polymers, such as polyvinyl alcohol        or polyvinylpyrrolidinone; and    -   inorganic thickening agents, in particular phyllosilicates such        as for example bentonite, particularly smectites, such as        montmorillonite or hectorite.

Coloring processes on keratin fibers conventionally take place in theweak acid to alkaline range, preferably in a weak acid to weak alkalineenvironment. In order to protect the keratin fibers and also the skin,it is not desirable to establish too high a pH. The pH of the agents canbe between 3 and 11, and preferably between 5 and 8. The pH values arepH values measured at a temperature of 22° C.

The alkalizing agents which can be used to establish the preferred pHare preferably selected from ammonia, alkanol amines, basic amino acidsas well as inorganic alkalizing agents. Preferred inorganic alkalizingagents include magnesium carbonate, sodium hydroxide, potassiumhydroxide, sodium silicate and sodium metasilicate. Organic alkalizingagents which can be used are preferably selected from monoethanolamine,2-amino-2-methylpropanol and triethanolamine. The basic amino acidswhich can be used as the alkalizing agent according to the invention arepreferably selected from the group comprising arginine, lysine,ornithine and histidine, particularly preferably arginine. Acidifyingagents which can be used to establish the pH are organic acids,including citric acid, acetic acid, ascorbic acid, benzoic acid, lacticacid, malic acid and maleic acid, as well as mineral acids such ashydrochloric acid, sulfuric acid or phosphoric acid.

It has furthermore proved advantageous for the coloring agents, inparticular if they additionally contain hydrogen peroxide, to contain atleast one stabilizer or complexing agent. Particularly preferredstabilizers include phenacetin, alkali benzoates (sodium benzoate) andsalicylic acid. All prior art complexing agents can moreover be used.Preferred complexing agents according to the invention arenitrogen-containing polycarboxylic acids, in particular EDTA and EDDS,and phosphonates, in particular 1-hydroxyethane-1,1-diphosphonate (HEDP)and/or ethylenediamine tetramethylene phosphonate (EDTMP) and/ordiethylenetriamine pentamethylene phosphonate (DTPMP) or the sodiumsalts thereof.

The agents can moreover contain further active agents, auxiliarysubstances and additives, including for example non-ionic polymers, likevinylpyrrolidinone/vinyl acrylate copolymers, polyvinylpyrrolidinone,vinylpyrrolidinone/vinyl acetate copolymers, polyethylene glycols andpolysiloxanes; additional silicones, such as volatile or non-volatile,straight-chain, branched or cyclic, crosslinked or uncrosslinkedpolyalkyl siloxanes (such as dimethicones or cyclomethicones), polyarylsiloxanes and/or polyalkylaryl siloxanes, in particular polysiloxaneshaving organofunctional groups, such as substituted or unsubstitutedamines (amodimethicones), carboxyl, alkoxy and/or hydroxyl groups(dimethicone copolyols), linear polysiloxane(A)-polyoxyalkylene(B) blockcopolymers, grafted silicone polymers; cationic polymers such asquaternized cellulose ethers, polysiloxanes having quaternary groups,dimethyldiallyl ammonium chloride polymers, acrylamide-dimethyldiallylammonium chloride copolymers, dimethylaminoethylmethacrylate-vinylpyrrolidinone copolymers quaternized with diethylsulfate, vinylpyrrolidinone-imidazolinium-methochloride copolymers andquaternized polyvinyl alcohol, in particular Polyquaternium-2,Polyquaternium-4, Polyquaternium-6, Polyquaternium-7, Polyquaternium-10,Polyquaternium-11, Polyquaternium-16, Polyquaternium-24,Polyquaternium-28, Polyquaternium-37, Polyquaternium-44,Polyquaternium-46, Polyquaternium-55, Polyquaternium-67,Polyquaternium-68, Polyquaternium-69 and Polyquaternium-87; zwitterionicand amphoteric polymers, such as in particular Polyquaternium-22 andPolyquaternium-39; structuring agents such as glucose, maleic acid andlactic acid, hair-conditioning compounds such as phospholipids, forexample lecithin and cephalins; perfume oils, dimethyl isosorbide andcyclodextrins; active agents to improve the fiber structure, inparticular mono-, di- and oligosaccharides such as for example glucose,galactose, fructose, fruit sugars and lactose; dyes for coloring theagent; anti-dandruff active agents such as piroctone olamine, zincomadine and climbazole; amino acids and oligopeptides; proteinhydrolysates of animal and/or plant origin as well as those in the formof their fatty acid condensation products or optionally anionically orcationically modified derivatives thereof; vegetable oils; lightstabilizers and UV blockers; active agents such as panthenol,pantothenic acid, pantolactone, allantoin, pyrrolidinone carboxylicacids and salts thereof as well as bisabolol; polyphenols, in particularhydroxycinnamic acids, 6,7-dihydroxycoumarins, hydroxybenzoic acids,catechins, tannins, leukoanthocyanidins, anthocyanidins, flavanones,flavones and flavonols; ceramides or pseudoceramides; vitamins,provitamins and vitamin precursors; plant extracts; fats and waxes suchas fatty alcohols, beeswax, montan wax and paraffins; swelling andpenetrating substances such as glycerol, propylene glycol monoethylether, carbonates, hydrogen carbonates, guanidines, ureas and primary,secondary and tertiary phosphates; opacifiers such as latex, styrene/PVPand styrene/acrylamide copolymers; pearlescent agents such as ethyleneglycol mono- and distearate and PEG-3 distearate; pigments as well aspropellants such as propane-butane mixtures, N₂O, dimethyl ether, CO₂and air.

A person skilled in the art can select these further substances inaccordance with the desired properties of the agents. With regard tofurther optional components and to the amounts of these components used,reference is expressly made to the relevant manuals known to a personskilled in the art, for example Kh. Schrader, Grundlagen and Rezepturender Kosmetika, 2^(nd) Edition, Hüthig Buch Verlag, Heidelberg, 1989. Theadditional active agents and auxiliary substances are used in the agentspreferably in amounts from 0.0001 to 25 wt. % in each case, inparticular from 0.0005 to 15 wt. %, relative to the total weight of theapplication mixture.

A method for coloring and optionally lightening keratinic fibers, inparticular human hair, wherein the agent of the first subject matter ofthe present technology is applied to the keratin-containing fibers, lefton the fibers for 5 to 60 minutes and then rinsed out again with wateror washed out with a shampoo, is suitable in particular for theapplication of the agents. The contact time of the ready-to-use coloringagents is preferably 5 to 45 minutes, in particular 10 to 40 minutes,particularly preferably 15 to 35 minutes. During the contact time of theagent on the fibers it can be advantageous to support the lighteningprocess by supplying heat. Heat can be supplied both from an externalheat source, for example hot air from a hot air blower, and also, inparticular if the hair lightening process is taking place on a livingtest subject, from the body temperature of the test subject. In thelatter case the section to be lightened is conventionally covered with ahood. A contact phase at room temperature is likewise contemplated aspart of the present technology. In particular, the temperature duringthe contact time is between 20° C. and 40° C., in particular between 25°C. and 38° C. After the end of the contact time the remaining coloringpreparation is rinsed out of the hair with water or a cleaning agent.Commercial shampoo can be used in particular as the cleaning agent, inparticular if the coloring agent has a carrier having a high surfactantcontent, then the cleaning agent can be dispensed with and the rinsingprocess can take place with water.

The agents can be formulated as one-component agents (coloring andlightening agent) or as multi-component agents such as two-componentagents or three-component agents, and used accordingly. A separationinto multi-component systems is useful in particular whereincompatibilities between the ingredients are to be expected or feared;in such systems the agent to be used is prepared by the consumerimmediately before use by mixing the components together.

If the agent contains both substantive dyes—as well as optionallyadditional oxidation dye precursors—and oxidizing agents, they areconveniently packaged separately from one another in order to avoid apremature, undesired reaction and brought into contact only immediatelybefore application.

A coloring method in which the coloring cream and the oxidizing agentare initially kept separate is therefore preferred. The presenttechnology therefore also provides a method for coloring and lighteninghuman hair, wherein a composition on an aqueous basis containinghydrogen peroxide is mixed with an agent according to the inventioncontaining at least one compound of formula (I) to form a homogeneouscomposition, and this is applied to the hair. The phosphate surfactant(b) can in this case be packaged both with the hydrogen peroxidesolution and with the compound of formula (I).

In a further embodiment of the present invention agents are thereforepreferred which are characterized in that they are produced immediatelybefore application by mixing at least two preparations, wherein the atleast two preparations are provided in at least two separately packagedcontainers, and wherein one container contains an agent (A), whichcontains in a cosmetic carrier at least one cationic anthraquinone dyeof formula (I) and at least one phosphate surfactant (b)—as well asoptionally additionally oxidation dye precursors, and a furthercontainer contains an oxidizing agent preparation (B) containing atleast one oxidizing agent.

The formulation of a combination of (a) compounds of general formula (I)with (b) the phosphate surfactants is outstandingly suitable forproducing intense colors with high brilliance, high shine and a lowselectivity in conjunction with an outstanding wash fastness.

Also provided is the use of an agent of the first subject matter of theinvention to produce hair dyes having increased shine, an intense colorresult with improved fastness properties and/or reduced selectivity.

All that has been stated in respect of the agents according to theinvention applies with necessary alterations to further preferredembodiments of the methods.

EXAMPLES

Formulation Example 1 wt. % Propylene carbonate 10.0 Ethanol, 96% 43.0D&C Red No. 33 0.05 Acid Black No. 1 0.005 D&C Orange No. 4 0.20 AcidViolet 43 0.030 Acid Red 18 0.20 Crodafos HCE-LQ 1.00 SME 253 3.50 Malicacid 0.40 Cationic Blue 347 0.20 Perfume qs Water to 100 Cationic Blue3473-[(4-amino-9,10-dihydro-3-methyl-9,10-dioxo-1-anthracenyl)amino]-N,N,N-trimethyl-1-propanaminiummethyl sulfate Crodafos HCE-LQ INCI name: Oleth-5 Phosphate, DioleylPhosphate (Croda) SME 253 approx. 26-33% active substance; INCI name:Amodimethicone, C11-15 Pareth-7, Laureth-9, Glycerin, Trideceth-12(Bayer Silicones)

What is claimed is:
 1. An agent for coloring or lightening a keratinicfiber, comprising, in a cosmetic carrier: (a) a compound of formula (I)

wherein R1, R2, and R3 each independently of one another denote ahydrogen, a halogen, a nitro group, a cyano group, a carboxyl group, asulfonic acid group, a hydroxyl group, a C₁-C₆ acyl amino group, acarboxamide group, a sulfonamide group, a C₁-C₆ alkyl group, C₁-C₆alkoxy group, a C₂-C₆ alkenyl group, a C₂-C₆ hydroxyalkyl group, or aC₁-C₆ alkoxy C₂-C₆ alkyl group; R4, R5, and R6 each independently of oneanother denote a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆hydroxyalkyl group, or a C₁-C₆ alkoxy C₂-C₆ alkyl group; X, Y, and Zeach independently of one another denote a hydrogen or an N(R7)(R8)group, wherein R7 and R8 each independently of one another denote ahydrogen, a C₁-C₆ alkyl group, a C₂-C₆ alkenyl group, a C₂-C₆hydroxyalkyl group, or a C₁-C₆ alkoxy C₂-C₆ alkyl group, and at leastone of the X, the Y and the Z denote an N(R7)(R8) group, n denotes anumber from 2 to 6; A⁻ denotes a physiologically acceptable anion; and(b) at least one phosphate surfactant.
 2. The agent of claim 1, whereinat least one of the R1, R2 and R3 denote a C₁-C₆ alkyl group.
 3. Theagent of claim 1, wherein X denotes an NH₂ group.
 4. The agent of claim1, wherein the compound of formula (I) comprises a compound according toa formula (Ia),

wherein the A⁻ denotes a physiologically acceptable anion.
 5. The agentof claim 1, wherein the compound of formula (I) is present in an amountof from 0.0001 to 5 wt. % of a total weight of the agent.
 6. The agentof claim 1, further comprising at least one of a C₈-C₃₀ alkyl phosphate,a C₈-C₃₀ alkyl ether phosphate, and a di(C₈-C₃₀ alkyl) phosphate.
 7. Theagent of claim 1, wherein the phosphate surfactant comprises a mixtureof at least one of a C₈-C₃₀ alkyl ether phosphate and a di(C₈-C₃₀alkyl)phosphate.
 8. The agent of claim 1, wherein the phosphatesurfactant is present in an amount of from 0.01 to 15 wt. %of a totalweight of the agent.
 9. The agent of claim 1, wherein the phosphatesurfactant comprises at least one of a compound selected from a groupcomprising: decyl phosphate, lauryl phosphate, C₁₂-C₁₃ alkyl phosphate,myristyl phosphate, cetyl phosphate, stearyl phosphate, isostearylphosphate, cetearyl phosphate, oleyl phosphate, and behenyl phosphate.10. The agent of claim 1, wherein the phosphate surfactant comprises atleast one of a compound selected from a group comprising: Deceth-3phosphate, Deceth-4 phosphate, Deceth-5 phosphate, Deceth-8 phosphate,Deceth-10 phosphate, Deceth-12 phosphate, Deceth-15 phosphate, Laureth-3phosphate, Laureth-4 phosphate, Laureth-5 phosphate, Laureth-8phosphate, Laureth-10 phosphate, Laureth-12 phosphate, Laureth-15phosphate, Ceteth-3 phosphate, Ceteth-4 phosphate, Ceteth-5 phosphate,Ceteth-8 phosphate, Ceteth-10 phosphate, Ceteth-12 phosphate, Ceteth-15phosphate, Steareth-3 phosphate, Steareth-4 phosphate, Steareth-5phosphate, Steareth-8 phosphate, Steareth-10 phosphate, Steareth-12phosphate, Steareth-15 phosphate, Ceteareth-3 phosphate, Ceteareth-4phosphate, Ceteareth-5 phosphate, Ceteareth-8 phosphate, Ceteareth-10phosphate, Ceteareth-12 phosphate, Ceteareth-15 phosphate, Oleth-3phosphate, Oleth-4 phosphate, Oleth-5 phosphate, Oleth-8 phosphate,Oleth-10 phosphate, Oleth-12 phosphate, Oleth-15 phosphate,PPG-3-Ceteth-10 phosphate, PPG-3-Ceteth-15 phosphate, PPG-5-Ceteth-10phosphate, PPG-5-Ceteth-15 phosphate, PPG-3-Oleth-10 phosphate,PPG-3-Oleth-15 phosphate, PPG-5-Oleth-10 phosphate, and PPG-5-Oleth-15.11. The agent of claim 1, wherein the phosphate surfactant comprises atleast one of a compound selected from a group comprising: didecylphosphate, dilauryl phosphate, di(C₁₂-C₁₃ alkyl)phosphate, dimyristylphosphate, dicetyl phosphate, distearyl phosphate, diisostearylphosphate, dicetearyl phosphate, dioleyl phosphate, and dibehenylphosphate.
 12. The agent of claim 1, wherein the phosphate surfactantcomprises a mixture of an Oleth-5 phosphate and a dioleyl phosphate. 13.The agent of claim 1, wherein the phosphate surfactant comprises amixture of a dicetyl phosphate and a Ceteth-10 phosphate.
 14. A methodfor coloring human hair, comprising: A. applying the agent as recited inclaim 1 to the hair; B. allowing the agent to act on the hair for aperiod from 5 to 45 minutes, preferably from 10 to 35 minutes; and C.rinsing the hair.